Polymers of hexahydrodiazaphosphorines or diazaphospholidines and silanes



United States Patent 3,304,270 POLYMERS 0F HEXAHYDRODIAZAPHOSPHQ- RINES0R DIAZAPHUSPHOLIDINES AND SILANES I Richard T. Dickerson, Midland,Mich., assignor to The Dow Chemical Company, Midland, Mich, acorporation of Delaware N0 Drawing. Filed Sept. 21, 1964, Ser. No.398,083 19 Claims. (Cl. 2602) This invention relates to new polymers anda process for preparation thereof. More specifically it relates to apolymer having a heterocyclic ring, partially inorganic, in the linearchain thereof. More specifically, this invention relates to polymershaving hexahydr-odiazaphosphorine or diazaphospholidine cyclic rings inthe linear chain thereof. For simplicity such rings are hereinaftersometimes referred to as diazaphosphorus rings.

The polymer products of this invention are capable of being formed intofibers and films and being used for various purposes appropriate forsuch shaped articles, such as textiles, clothing, protective coatings,etc.

The polymers of this invention are prepared by the reaction of theheterocyclic compound or diazaphosphorus ring compounds of the formulawherein n is 2 or 3; R is hydrogen or an alkali metal such as Na, K orLi; R is NR OR" or R" group, and R" is an aliphatic, cycloaliphatic oraromatic hydrocarbon group having no more than 20, preferably no morethan 6 carbon atoms. These compounds and the preparation thereof aredisclosed in applicants copending application Serial No. 398,069 filedthe same date herewith.

To form the polymers of this invention, the heterocyclic compounds arecondensed by reaction with one or more condensing reagents of theformula: SiX wherein X is .a halogen atom, e.g. Cl, Br, I or F, or an R"or OR" radical in which R" is as defined above and the reagent containsat least two halogen atoms.

The new polymers of this invention are represented by the formula Whereonly two X groups are replaced by the heterocyclic compounds theresultant polymers are linear. Where 3,364,270 Patented Feb. 14, 1967more than two X groups are so replaced, the resultant polymers arebranched or crosslinked between linear chains by such diazaphosphorusrings.

Typical condensing reagents of the formula given above are siliconhalide, hydrocarbon and oxyhydrocarbon derivatives, such as SiCl SiBrSiI Si(CH Cl 2 5)2 2 5 11)z z, 2( 2 5)2 s s,

Typical hydrocarbon groups that can be used for R and R" include:methyl, ethyl, propyl, butyl, amyl, heXyl, octyl, decyl, octadecyl,dodecyl, vinyl, allyl, butenyl, butadienyl, cycl-ohexyl, propargyl,cyclopentyl, cyclohexenyl, cyclopentadienyl, methyl cyclohexyl, ethylcyclohexyl, methyl cyclopentyl, pentyl, tolyl, xylyl, ethyl phenyl,propyl phenyl, butyl phenyl, naphthyl, methyl naphthyl, ethyl naphthyl,octyl naphthyl, diphenyl, methyl diphenyl, ethyl diphenyl, etc.

Typical oxhydrocarbon radicals than can be used for R include: methoxy,ethoxy, butoxy, hexoxy, octoxy, vinyloxy, allyloxy, butenyloxy,butadienyloxy, propargyloxy, cyclohexyloxy, cyclopentoxy, methylcyclohexoxy, methyl cyclopentoxy, phenoxy, tolyloxy, xylyloxy,naphthoxy, methylnaphthoxy, diphenyloxy, etc.

A typical heterocyclic starting material used in preparing the polymersof this invention is Z-diphenylarnino- 1,3,2-diazaphospholidine-2-oxidewhich has the formula Another typical starting compound is2-diphenylaminohexahydro-1,3,2-diazaphosphorine-Z-oxide which has theformula CH3 CH2 OH:

NH NH O N (00 02 Other typical starting compounds are disclosedhereinafterk These cyclic compounds can be used as such or in the formof the alkali metal derivatives in which one or both of the hydrogensattached to the ring nitrogen atoms have been replaced by Na, K or Li.As previously indicated, various diazaphospholidineoxides andhexahydro-1,3,Z-diazaphosphorine-oxides suitable for use in the practiceof this invention and methods of preparation are disclosed in applicantscopending application Serial No. 398,069, filed the same date herewith.However, the methods of preparation are illustrated by the followingexamples which are typical for the various related compounds.

EXAMPLE I A solution of 48 parts ethylene diamine in 500 parts ofmethylene chloride is prepared by stirring a mixture thereof. Thesolution is cooled to 5 C. in an ice bath and then to this is addeddropwise a filtered solution of 22 parts diphenyl-phosphoramidicdichloride in 300 parts of methylene chloride over a period of about 4hours. The mixture is then permitted to stand overnight. From this theprecipitated solids are filtered, and the filtrate is evaporated torecover the solute. There is thus obtained a product which whenrecrystallized from 2-propanol gives a recovery of 25 parts having amelting point of 182 C. The precipitated solids recovered by thefiltering operation are extracted with water to remove amine salt, andthen dried. This residue amounts to 57 parts and has a melting point ofapproximately 177 C. This product is insoluble in methylene chloride inits recovered form. However, upon being dissolved in methanol and thenrecovered by evaporation of the methanol, the recovered solid is solublein methylene chloride and is identical to the solute recovered from theevaporated filtrate. The apparent dilference in methylene chloridesolubility of the crude material is believed to be due to a differencein crystalline form as compared with the same compound recovered fromthe methylene chloride solution. This product is identified asZ-diphenylamino-1,3,2-diazaphospholidine-Z-oxide and is the compoundused in a number of examples hereinafter for preparation of polymericmaterials.

EXAMPLE II The procedure of the preceding example is. repeated exceptthat an equivalent amount of 1,3-propane diamine is used in place of theethylene diamine. The Z-diphenylamino-hexahydro-1,3,2-diazaphosphorineoxide product has a melting point of l69170 C. When the procedure isrepeated using phosphoryl dihalides (RPOCl with dilferent R groupsrespectively, the corresponding products are obtained such as forexample:

2-phenyl-hexahydro-1,3,2-diazaphosphorine oxide having a melting pointof 138141 C.;

Z-dimethylarnino-hexahydro 1,3,2 diazaphosphorine oxide having a meltingpoint of 127-130 C.;

2-methyl-hexahydro-1,3,2-diazaphosphorine oxide having a melting pointof 116-121 C.

EXAMPLE III With the reaction temperature maintained at 15 C., asolution of 105 parts of phenyl phosphorodichloridate in 200 parts ofchloroform is added with stirring to a solution of 82 parts1,3-propanediamine in 600 parts of chloroform. The resultant solution isallowed to stand at room temperature overnight. After precipitatedsolids are re moved by filtration, the product is recovered from thefiltrate by evaporation of the solvent. A crude yield of 33 parts isthus obtained. Upon recrystallization from ethyl acetate, the product isfound to melt at 145.5 C. and is identified ashexahydro-Z-phenoxy-1,3,2-diazaphosphorine-Z-oxide. Additional productis recovered from the original filter cake by extraction with ethyl.acetate.

By using an equivalent amount of methyl phosphorodichloridate in placeof the phenyl compound used above, thehexahydro-Z-methoxy-1,3,2-diazaphosphorine-Z-oxide is obtained having amelting point of 86-89 C. after crystallization from toluene.

The above procedures can be used in preparing all the variousdiazaphosphorus cyclic ring compounds for use in the practice of thisinvention by using phosphoryl dihalides in which the diphenylaminoradical of the phosphoryl dihalide used in Examples I and II is replacedby various --NR" NHR", OR" and R" radicals as defined and illustratedabove for the R radical.

By these procedures, the following typical compounds are prepared:

2-dimethy1amino-hexahydro-1,3,2-diazaphosphorine- 2-oxide 2dicyclohexylamino-hexahydro-1,3,2-diazaphosphorine- 2-oxideZ-dibenzylamino-hexahydro-1,3,2-diazaphosphorine- 2-oxideZ-ethyl-hexahydrol ,3,2-diaZaphosphorine-Z-oxideZ-amyl-hexahydro-1,3,2-diazaphosphorine-Z-oxideZ-phenyl-hexahydro-1,3,Z-diazaphosphorine-Z-oxideZ-cyclopentyl-hexahydro-l ,3,2-diazaphosphorine-Z-oxideZ-naphthyl-hexahy-dro- 1 ,3,2-diazaphosphorine2-oxideZ-methyl-hexahydro-l ,3,2-diazaphosphorine-2-oxideZ-cyclohexyl-hexahydro-1,3 ,Z-diazaphosphorine-Z-oxide2-tolyl-hexahydro-1,3,2-diazaphosphorine-2-oxide Z-butyl-hexahydrol ,3,2-diazaphosphorine2oxide2-octyl-hexahydro-1,3,2-diazaphosphorine-Z-oxide2-allyl-hexahydro-1,3,2-diazaphosphorine-2-oxide2-(p-allylphenyl)-hexahydro-1,3,2-diazaphosphorine- 2-oxide2-cyclopentadienyl-hexahydro-1,3,2-diazaphosphorine- Z-oxideZ-butadicnyl-hexahydrol ,3,2-diazaphosphorine-2-oxide2'-propargyl-hexahydro-1,3,Z-diazaphosphorine-2-oxide2-cyclohexenyl-hexabydro-1,3,2-diazaphosphorine- 2-oxideZ-methoxy-hexahydro-l ,3,2-diazaphosphorine-2-oxideZ-phenoxy-hexahydro-1,3,Z-diazaphosphorine-2-oxide2-cyclohexoxy-hexahydro-1,3,Z-diazaphosphorine-Z-oxideZ-butoxy-hexahydrol ,3 ,2-diazaphosphorine-Z-oxide2-allyloxy-hexahydro-l,3,2-diazaphosphorine-2-oxide2-tolyloxy-hexahydro-l ,3,2-diazaphosphorine-2-oxideZ-dimethylarnino-l,3,Z-di-azaphospholidine-2-0xideZ-dicyclohexylamino-l,3,2-diazaphospholidine-2-oxide Z-dibenzylaminol,3,2-diazaphospholidine-Z-oxide Z-ethyl-l,3,Z-diazaphospholidine-Z-oxide Z-amyl-l,3,2-diazaphospholidine-2-oxide2-phenyll ,3,2-diazaphospholidine-2-oxide Z-cyclopentyll,3,2-diazaphospholidine-Z-oxide2-naphthyl-1,3,Z-diazaphospholidine-2-oxidcZ-methyl-1,3,2-diazaphospholidine-2-oxide Z-cyclohexyll,3,2-diazaphospholidine-Z-oxide Z-tolyl-1,3,2-diazaphospholidine-Z-oxideZ-butyll ,3,2-diazaphospholidineJ-oxide 2-octyl-1,3,2--diazaphospholidine-2-oxide 2 allyl-l ,3,Z-diazaphospholidine-Z-oxide 2-(p-allylphenyl)-l,3,Z-diazaphospholidine-Z-oxide 2-cy-clopentadienyl- 1,3,Z-diazaphospholidine-Z-oxideZ-butadienyll,3,Z-diazaphospholidine-Z-oxideZ-propargyl-1,3,Z-diazaphospholidine-Z-oxide 2-cyclohexenyl-1,3,2-diazaphospholidine-Z-oxide 2-methoxy- 1,3,2-diazaphospholidine-Z-oxide Z-phenoxy- 1,3,Z-di-azaphospholidine-Z-oxide2-cyclohexoxy-1,3,2-diazaphospholidine-Z-oxideZ-butoxy-1,3,Z-diazaphospholidine-Z-oxide2-allyloxy-1,3,Z-diazaphospholidine-2-oxide Z-t-olyloxy-l ,3,Z-diazaphospholidine-Z-oxide the scope of the invention nor the mannerin which the invention can be practiced. Unless specifically indicatedotherwise, here and throughout the specification, parts and percentagesare given by weight.

EXAMPLE IV A solution of 2.7 partsZ-diphenylamino-1,3,2-diazaphospholidine-Z-oxide and 2 parts triethylamine is prepared in 25 parts of chloroform. To this solution is addeddropwise with stirring 1.3 parts dichlorodimethyl silane. After theaddition is completed, the solution is permitted to stand overnightduring which time the color darkens. The product is then extracted withan equal volume of water, the water layer separated and the chloroformlayer evaporated. From the chloroform layer is obtained about 3 parts ofa clear, amber resinous product which can be drawn into fibers and castin a film from chloroform solution. The infra-red spectrum of this filmshows reduction in intensity of the N-H band at 3n and appearance ofbands at about 10,41. which are in the region where Si-N absorptionshould occur.

P suorrmcli (C2H5)aN The procedure of Example IV is repeated except thatin place of the diazaphospholidine there is used 2.8 parts of2-diphenylamino-hexahydro-1,3,2-diazaphosphorine-2- oxide. The infraredspectra of the product shows similar eifects and is consistent with theformation of the follow- EXAMPLE v1 The monolithium salt of2-diphenylamino-l,3,2-diaza phospholidine-Z-oxide is prepared using 2.78parts of the oxide and 1.21 parts of butyl lithium in sodium-driedbenzene. To this is added a solution of 0.95 parts of silicontetrachloride in 100 parts of hexane. The reaction is vigorous andresults in the precipitation of a dark brown and soluble solid which isindicated to be the dimer,

P mcurm 0 N( a )2 This dimer is further polymerized by the addition of ahydrogen chloride acceptor (triethylamine) and additional SiCL; to givea polymer of the formula:

NH l J 0 N(C&H5)2 X 0 N(C H5)g EXAMPLE VII The dimer and higher polymerof Example VI are prepared by repeating the procedure of Example VIusing the corresponding monosodium salt prepared by reaction of theheterocyclic base with NaNH in an inert solvent such as benzene.

EXAMPLE VIII The dimer and higher polymer of Example VI are prepared byrepeating the procedure of Example VI with the correspondingmonopotassium salt of the heterocyclic base prepared with KNI-I in aninert solvent such as benzene.

EXAMPLE IX The procedures of Examples IV-VIII are repeated using inplace of the diazaphosphorus compound of the respective examples thecorresponding compounds in which the diphenylamino group is replaced bythe following groups:

In each case the resultant polymer corresponds in the polymericstructure to that shown in the respective examples except that therepeating units of the polymer and in the diazaphosphorus end group hasthe diphenylamino group replaced by the respective R groups recitedabove.

For example, the following typical specific polymers are obtained:

CH;CH; H-N NSi(CI-I3)2N NH /CE2 C52 ?Hg (EH2 I $2 (EH1 H-N NSi(CHa)z-NNH J morn x o N(CH3)2 |"]CHz-([JH CHzCHz H-N\ O/ X O/ N( 2 s)2 CH2 [0CH3 CH3 CH3 2-N NH L x j 0 molar), x o M02115): PEE -CH I CH-.-OH M O/N(O5H11)2 x O/ N( eHn):

H-N N S1(CH3)EN NH O/ 00H}; X O/ 05135 I 1 C62 \?H2 HN. NS'1(CH3)2-N NHEXAMPLE X The procedures of the preceding Example IV-VIII pound in whichthe diphenylamino group has been replaced by methyl, butyl, octyl,allyl, cyclohexyl, phcnyl,

allyloxy radicals, respectively. In each case, the structure of theresultant polymer corresponds to that of the reis replaced in therepeating unit and in the terminal diazaphosphorus radical by therespective radicals listed I"?H7OH2 N( a)2 N( a)2 NSi(CHa)2-N NH OH: I 1i HN NS1(CH HN N-Si (C H3) 2N\ NH CHz-CH CHz-CH I l /CE 01h [CH 0H: t jo 0011 x o OOH;

are repeated using in each case a diazaphosphorus comnaphthyl, ethoxy,hexoxy, cyclohexyloxy, phenoxy and spective examples except that thediphenylamino radical above.

7 EXAMPLE XI The procedure of Example IV is repeated using the followingcoupling agents in equivalent amounts in place of the dichlorodirnethylsilane:

and Si(CH Br respectively. In each case, the resultant polymer has aconnecting link between the diazaphosphorus rings corresponding to therespective coupling agents substituted for the dichlorodimethyl silane.

'While the polymeric structures defined above are represented as linearpolymers, the polymers can actually be crosslinked in view of thetrifunctional or tetrafunctional character of some of the couplingagents.v The freedom or presence of crosslinking in the respectivepolymers and the degree of such crosslinking can be controlled byvarious means. For example, the proportions of diazaphosphorus compoundcan be restricted so that there is only sufficient to react with onlytwo valences of the coupling agent, preferably with the diazaphosphoruscompound being added to the coupling agent. Also, the substituent groupson the coupling agent can be of different degrees of reactivity so thatthe reaction is preferentially with the more reactive or more easilydisplaced substituent groups. Such is the case with dichlorodimethylsilane and dichlorodiethyl silane.

The reactivity of the respective reagents described herein is sulficientto cause the desired reaction without any particular conditions beingrequired to promote the reaction. Generally, however, the reaction isfavored by a temperature of at least room temperature and no unfavorableresults are occasioned by having the temperature as high as 100 C.except that provisions should be made for absorption of heat where thereaction is exceedingly exothermic. Except as described above withrespect to hydrogen halide acceptors, no particular catalysts orinitiators are required to promote the reaction. In most cases, in viewof the reactivity of the respective coupling agents, it is desirable tohave the reagents and reaction mixture in an anhydrous condition.Generally, atmospheric pressure is suitable, although no disadvantage isseen in the application of superatmospheric pressures.

A previously indicated, the polymers of this invention include dimers,namely, those having two of the diazaphosphorus ring structures thereinup to molecular weights of 50,000 and even higher, depending on theparticular properties desired in the resultant polymers. Solventssuitable for use in conducting the reactions will vary according to theparticular reagents being used. In many cases, the polymer products aresoluble in the solvent used for the reagents. However, this depends onthe amount of crosslinking and the nature of the polymer. Solventssuitable for many of the reactions include: methylene chloride,chloroform, ethylene chloride, trichloroethane, etc.

While certain features of this invention have been described in detailwith respect to variousembodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention and it is not intended to limit the invention tothe exact details shown above except insofar as they are defined in thefollowing claims:

The invention claimed is:

1. A polymer consisting essentially of a structure having the formulawherein 2. A polymer consisting essentially of a structure having theformula (Err-CH2 I CHz-CH2 wherein x is an integer of at least 1.

3. A polymer consisting essentially of a structure having the formulawherein x is an integer of at least 1.

4. A polymer consisting essentially of a structure having the formula OH; C H: ?a CH1 1 C oHi Hl l IllSiCl2-N l IH wherein x is an integer ofat least 1.

5. A polymer consisting essentially of a structure having the formulawherein x is an integer of at least 1.

6. A polymer consisting essentially of a structure having the formulawherein at is an integer of at least 1.

7. A polymer consisting essentially of a structure having the formulawherein is an integer of at least 1.

8. A polymer consisting essentially of a structure having the formulawherein x is an integer of at least 1.

9. A polymer consisting essentially of a structure having the formulawherein x is an integer of at least 1.

10. The process of preparing a polymeric composition comprising thesteps of reacting (a) a heterocyclic compound of the formula n is aninteger having a value of at least 2 and no more than 3; (b) with acoupling reagent of the formula SiX wherein X is selected from the classconsisting of halogen atoms and R" and OR, said reagent having at leasttwo halogen atoms therein.

11. The process of claim 10 in which said coupling reagent is SiCl 12.The process of claim 11 in which said heterocyclic compound is2-dipheny1amino-hexahydro-l,3,2-diazaphos phorine-Z-oxide.

13. The process of claim 1.1 in which said heterocyclic compound isZ-diphenylamino-1,3,Z-diazaphospholidine- 2-oxide.

14. The process of claim 10 in which said coupling agent isdichlorodimethyl silane.

15. The process of claim 14 in which said heterocyclic compound is2-diphenylamino-hexahydro-1,3,2-diazaphosphorine-Z-oxide.

16. The process of claim 14 in which said heterocyclic compound isZ-diphenylamino-1,3,Z-diazaphospholidine-Z- oxide.

17. The process of claim 10 in which said coupling agent is methylsilane trichloride.

18. The process of claim 10 in which said coupling agent isdichlorodiethyl silane.

19. The process of claim 10 in Which said coupling agent is ethyl silanetrichloride.

References Cited by the Examiner Autenrieth et 211., Berichte derDeutschen Chem. Gesellschaft, vol. 58, p. 2144-2150 (1925).

SAMUEL H. BLECH, Primary Examiner.

1. A POLYMER CONSISTING ESSENTIALLY OF A STRUCTURE HAVING THE FORMULA10. THE PROCESS OF PREPARING A POLYMERIC COMPOSITION COMPRISING THESTEPS OF REACTING (A) A HETEROCYCLIC COMPOUND OF THE FORMULA